U.S. patent application number 10/566940 was filed with the patent office on 2006-12-07 for fuel cell membrane containing zirconium phosphate.
Invention is credited to Zhen-Yu Yang.
Application Number | 20060275636 10/566940 |
Document ID | / |
Family ID | 33490664 |
Filed Date | 2006-12-07 |
United States Patent
Application |
20060275636 |
Kind Code |
A1 |
Yang; Zhen-Yu |
December 7, 2006 |
Fuel cell membrane containing zirconium phosphate
Abstract
The present invention provides for a compound having the
following structure:
Zr(O.sub.3PZ.sub.qY.sub.nX).sub.2-m(03PR).sub.m, wherein X=a
functional group such as CO.sub.2H, PO(OH).sub.2, and SO.sub.3H,
and SO.sub.2NHSO.sub.2W, wherein W=aryl of 6 to 10 carbon atoms or
Y; Y=perfluoro-linear, branched or cyclic alkylene group, wherein
the alkylene is 1-20 carbon atoms, or a fluorinated group
containing at least one substituent selected from the group
consisting of oxygen, chlorine and bromine; Z=alkylene of 1-12
carbon atoms, aryl of 6-10 carbon atoms, or a heterocyclic aryl
group of 3-10 carbons atoms; R=alkyl of 1-12 carbon atoms, aryl of
6-10 carbon atoms, substituted alkyl, or substituted aryl, wherein
the substituent is selected from the group consisting of F, Cl,
perfluoroalkyl, alkyl of 1-12 carbon atoms and aryl of 6-10 carbon
atoms; n=0 or 1; q=0 or 1; and m=0 to 1.5; with the proviso that
when n=0, and q=1, Z=at least one heterocyclic group having 3 to 10
carbon atoms, 1 to 5 nitrogen atoms and 0 to 4 oxygen atoms. The
invention also provides a polymer electrolyte membrane, a catalyst
coated membrane and a fuel cell having this compound.
Inventors: |
Yang; Zhen-Yu; (Hockessin,
DE) |
Correspondence
Address: |
E I DU PONT DE NEMOURS AND COMPANY;LEGAL PATENT RECORDS CENTER
BARLEY MILL PLAZA 25/1128
4417 LANCASTER PIKE
WILMINGTON
DE
19805
US
|
Family ID: |
33490664 |
Appl. No.: |
10/566940 |
Filed: |
May 21, 2004 |
PCT Filed: |
May 21, 2004 |
PCT NO: |
PCT/US04/16431 |
371 Date: |
February 13, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60473870 |
May 27, 2003 |
|
|
|
Current U.S.
Class: |
429/481 ;
429/306; 429/494; 429/506; 429/516; 556/52; 568/14; 568/15;
568/17 |
Current CPC
Class: |
H01M 8/1004 20130101;
H01M 8/1009 20130101; C07F 9/4006 20130101; C07F 9/65068 20130101;
H01M 8/1016 20130101; C07F 9/3808 20130101; C07F 9/65031 20130101;
C07F 9/4037 20130101; C07F 9/3856 20130101; C07F 9/65312 20130101;
C07F 9/6506 20130101; Y02E 60/50 20130101 |
Class at
Publication: |
429/033 ;
429/306; 568/014; 568/015; 568/017; 556/052 |
International
Class: |
H01M 8/10 20060101
H01M008/10; H01M 10/36 20060101 H01M010/36; C07F 9/02 20060101
C07F009/02; C07F 7/28 20060101 C07F007/28 |
Claims
1. A compound having the following structure:
Zr(O.sub.3PZ.sub.qY.sub.nX).sub.2-m(O.sub.3PR).sub.m wherein X=a
functional group selected from the group consisting of CO.sub.2H,
PO(OH).sub.2, SO.sub.3H, and SO.sub.2NHSO.sub.2W, wherein W=aryl of
6 to 10 carbon atoms or Y; Y=perfluoro-linear, branched or cyclic
alkylene group, wherein the alkylene is 1-20 carbon atoms, or a
fluorinated group containing at least one substituent selected from
the group consisting of oxygen, chlorine and bromine; Z=alkylene of
1-12 carbon atoms, aryl of 6-10 carbon atoms, or a heterocyclic
aryl group of 3-10 carbons atoms; R=alkyl of 1-12 carbon atoms,
aryl of 6-10 carbon atoms, substituted alkyl, or substituted aryl,
wherein the substituent is selected from the group consisting of F,
Cl, perfluoroalkyl, alkyl of 1-12 carbon atoms and aryl of 6-10
carbon atoms; n=0 or 1; q=0 or 1; and m=0 to 1.5; with the proviso
that when n=0, and q=1, Z=at least one heterocyclic group having 3
to 10 carbon atoms, 1 to 5 nitrogen atoms and 0 to 4 oxygen
atoms.
2. The compound of claim 1 wherein Y=perfluoro-linear, branched or
cyclic alkylene group, wherein the alkylene is selected from the
group consisting of perfluoromethylene, perfluoroethylene and
perfluoropropylene.
3. The compound of claim 1 wherein Y is
CF.sub.2CF.sub.2OCF.sub.2CF.sub.2 or
CF.sub.2CFCF.sub.3OCF.sub.2CF.sub.2.
4. The compound of claim 1 wherein Z=a heterocyclic aryl group
comprising 3 to 8 carbon atoms, 1 to 5 nitrogen atoms, and 0 to 4
oxygen atoms.
5. The compound of claim 4 wherein the heterocyclic aryl group
comprises 3 to 8 carbon atoms, 2 to 3 nitrogen atoms, and 0 to 2
oxygen atoms.
6. The compound of claim 4 wherein Z is selected from the group
consisting of benzimidazole, imidazole, pyrazole, triazole,
thiazole, and oxadiazole.
7. The compound of claim 1 wherein R is selected from the group
consisting of methyl, ethyl, propyl, butyl and phenyl.
8. The compound of claim 1 selected from the group consisting of
Zr(HO.sub.2CCF.sub.2CH.sub.2CH.sub.2CH.sub.2PO.sub.3).sub.2,
Zr(H.sub.2O.sub.3PCF.sub.2CH.sub.2CH.sub.2CH.sub.2PO.sub.3).sub.2,
Zr(HO.sub.3SCF.sub.2CF.sub.2OCF.sub.2CF.sub.2CH.sub.2CH.sub.2CH.sub.2PO.s-
ub.3).sub.2, Zirconium(2-benzimidazolyl-2-ethylphosphonate),
Zirconium(2-imidazolyl-2-ethylphosphonate),
Zirconium(2-pyrazolyl-2-ethylphosphonate), and
Zirconium(2-oxadiazolyl-2-ethylphosphonate).
9. A functionalized phosphonic acid having the following structure:
(HO).sub.2OPZ.sub.qY.sub.nX. wherein X=a functional group selected
from the group consisting of CO.sub.2H, PO(OH).sub.2, SO.sub.3H,
and SO.sub.2NHSO.sub.2W, wherein W=aryl of 6 to 10 carbon atoms or
Y; Y=perfluoro-linear, branched or cyclic alkylene group, wherein
the alkylene is 1-20 carbon atoms, or a fluorinated group
containing at least one substituent selected from the group
consisting of oxygen, chlorine and bromine; Z=alkylene of 1-12
carbon atoms, aryl of 6-10 carbon atoms, or a heterocyclic aryl
group of 3-10 carbons atoms; n=0 or 1; and q=0 or 1; with the
proviso that when n=0, and q=1, Z=at least one heterocyclic group
having 3 to 10 carbon atoms, 1 to 5 nitrogen atoms and 0 to 4
oxygen atoms.
10. A solid electrolyte membrane comprising a compound having the
following structure:
Zr(O.sub.3PZ.sub.qY.sub.nX).sub.2-m(O.sub.3PR).sub.m wherein X=a
functional group selected from the group consisting of CO.sub.2H,
PO(OH).sub.2, SO.sub.3H, and SO.sub.2NHSO.sub.2W, wherein W=aryl of
6 to 10 carbon atoms or Y; Y=perfluoro-linear, branched or cyclic
alkylene group, wherein the alkylene is 1-20 carbon atoms, or a
fluorinated group containing at least one substituent selected from
the group consisting of oxygen, chlorine and bromine; Z=alkylene of
1-12 carbon atoms, aryl of 6-10 carbon atoms, or a heterocyclic
aryl group of 3-10 carbons atoms; R=alkyl of 1-12 carbon atoms,
aryl of 6-10 carbon atoms, substituted alkyl, or substituted aryl,
wherein the substituent is selected from the group consisting of F,
Cl, perfluoroalkyl, alkyl of 1-12 carbon atoms and aryl of 6-10
carbon atoms; n=0 or 1; q=0 or 1; and m=0 to 1.5; with the proviso
that when n=0, and q=1, Z=at least one heterocyclic group having 3
to 10 carbon atoms, 1 to 5 nitrogen atoms and 0 to 4 oxygen
atoms.
11. The solid electrolyte membrane of claim 10 further comprising a
porous support.
12. The solid electrolyte membrane of claim 10 wherein
Y=perfluoro-linear, branched or cyclic alkylene group, wherein the
alkylene is selected from the group consisting of
perfluoromethylene, perfluoroethylene and perfluoropropylene.
13. The solid electrolyte membrane of claim 10 wherein Y is
CF.sub.2CF.sub.2OCF.sub.2CF.sub.2 or
CF.sub.2CFCF.sub.3OCF.sub.2CF.sub.2.
14. The solid electrolyte membrane of claim 10 wherein Z=a
heterocyclic aryl group comprising 3 to 8 carbon atoms, 1 to 5
nitrogen atoms, and 0 to 4 oxygen atoms.
15. The solid electrolyte membrane of claim 14 wherein the
heterocyclic aryl group comprises 3 to 8 carbon atoms, 2 to 3
nitrogen atoms, and 0 to 2 oxygen atoms.
16. The solid electrolyte membrane of claim 14 wherein Z is
selected from the group consisting of benzimidazole, imidazole,
pyrazole, triazole, thiazole, and oxadiazole.
17. The solid electrolyte membrane of claim 10 wherein R is
selected from the group consisting of methyl, ethyl, propyl, butyl
and phenyl.
18. The solid electrolyte membrane of claim 10 wherein the compound
is selected from the group consisting of
Zr(HO.sub.2CCF.sub.2CH.sub.2CH.sub.2CH.sub.2PO.sub.3).sub.2,
Zr(H.sub.2O.sub.3PCF.sub.2CH.sub.2CH.sub.2CH.sub.2PO.sub.3).sub.2,
Zr(HO.sub.3SCF.sub.2CF.sub.2OCF.sub.2CF.sub.2CH.sub.2CH.sub.2CH.sub.2PO.s-
ub.3).sub.2, Zirconium(2-benzimidazolyl-2-ethylphosphonate),
Zirconium(2-imidazolyl-2-ethylphosphonate),
Zirconium(2-pyrazolyl-2-ethylphosphonate), and
Zirconium(2-oxadiazolyl-2-ethylphosphonate).
19. A catalyst coated membrane comprising a solid electrolyte
membrane having a first surface and a second surface, an anode
present on the first surface of the solid electrolyte membrane, and
a cathode present on the second surface of the solid electrolyte
membrane, wherein the solid electrolyte membrane comprises a
compound having the following structure:
Zr(O.sub.3PZ.sub.qY.sub.nX).sub.2-m(O.sub.3PR).sub.m wherein X=a
functional group selected from the group consisting of CO.sub.2H,
PO(OH).sub.2, SO.sub.3H, and SO.sub.2NHSO.sub.2W, wherein W=aryl of
6 to 10 carbon atoms or Y; Y=perfluoro-linear, branched or cyclic
alkylene group, wherein the alkylene is 1-20 carbon atoms, or a
fluorinated group containing at least one substituent selected from
the group consisting of oxygen, chlorine and bromine; Z=alkylene of
1-12 carbon atoms, aryl of 6-10 carbon atoms, or a heterocyclic
aryl group of 3-10 carbons atoms; R=alkyl of 1-12 carbon atoms,
aryl of 6-10 carbon atoms, substituted alkyl, or substituted aryl,
wherein the substituent is selected from the group consisting of F,
Cl, perfluoroalkyl, alkyl of 1-12 carbon atoms and aryl of 6-10
carbon atoms; n=0 or 1; q=0 or 1; and m=0 to 1.5; with the proviso
that when n=0, and q=1, Z=at least one heterocyclic group having 3
to 10 carbon atoms, 1 to 5 nitrogen atoms and 0 to 4 oxygen
atoms.
20. The catalyst coated membrane of claim 19 wherein the solid
electrolyte membrane further comprising a porous support.
21. The catalyst coated membrane of claim 19 wherein
Y=perfluoro-linear, branched or cyclic alkylene group, wherein the
alkylene is selected from the group consisting of
perfluoromethylene, perfluoroethylene and perfluoropropylene.
22. The catalyst coated membrane of claim 19 wherein Y is
CF.sub.2CF.sub.2OCF.sub.2CF.sub.2 or
CF.sub.2CFCF.sub.3OCF.sub.2CF.sub.2.
23. The catalyst coated membrane of claim 19 wherein Z=a
heterocyclic aryl group comprising 3 to 8 carbon atoms, 1 to 5
nitrogen atoms, and 0 to 4 oxygen atoms.
24. The catalyst coated membrane of claim 23 wherein the
heterocyclic aryl group comprises 3 to 8 carbon atoms, 2 to 3
nitrogen atoms, and 0 to 2 oxygen atoms.
25. The catalyst coated membrane of claim 23 wherein Z is selected
from the group consisting of benzimidazole, imidazole, pyrazole,
triazole, thiazole, and oxadiazole.
26. The catalyst coated membrane of claim 19 wherein R is selected
from the group consisting of methyl, ethyl, propyl, butyl and
phenyl.
27. The catalyst coated membrane of claim 19 wherein the compound
is selected from the group consisting of
Zr(HO.sub.2CCF.sub.2CH.sub.2CH.sub.2CH.sub.2PO.sub.3).sub.2,
Zr(H.sub.2O.sub.3PCF.sub.2CH.sub.2CH.sub.2CH.sub.2PO.sub.3).sub.2,
Zr(HO.sub.3SCF.sub.2CF.sub.2OCF.sub.2CF.sub.2CH.sub.2CH.sub.2CH.sub.2PO.s-
ub.3).sub.2, Zirconium(2-benzimidazolyl-2-ethylphosphonate),
Zirconium(2-imidazolyl-2-ethylphosphonate),
Zirconium(2-pyrazolyl-2-ethylphosphonate), and
Zirconium(2-oxadiazolyl-2-ethylphosphonate).
28. A fuel cell comprising a solid electrolyte membrane having a
first surface and a second surface, wherein the solid electrolyte
membrane comprises a compound having the following structure:
Zr(O.sub.3PZ.sub.qY.sub.nX).sub.2-m(O.sub.3PR).sub.m wherein X=a
functional group selected from the group consisting of CO.sub.2H,
PO(OH).sub.2, SO.sub.3H, and SO.sub.2NHSO.sub.2W, wherein W=aryl of
6 to 10 carbon atoms or Y; Y=perfluoro-linear, branched or cyclic
alkylene group, wherein the alkylene is 1-20 carbon atoms, or a
fluorinated group containing at least one substituent selected from
the group consisting of oxygen, chlorine and bromine; Z=alkylene of
1-12 carbon atoms, aryl of 6-10 carbon atoms, or a heterocyclic
aryl group of 3-10 carbons atoms; R=alkyl of 1-12 carbon atoms,
aryl of 6-10 carbon atoms, substituted alkyl, or substituted aryl,
wherein the substituent is selected from the group consisting of F,
Cl, perfluoroalkyl, alkyl of 1-12 carbon atoms and aryl of 6-10
carbon atoms; n=0 or 1; q=0 or 1; and m=0 to 1.5; with the proviso
that when n=0, and q=1, Z=at least one heterocyclic group having 3
to 10 carbon atoms, 1 to 5 nitrogen atoms and 0 to 4 oxygen
atoms.
29. The fuel cell of claim 28 further comprising an anode and a
cathode present on the first and second surfaces of the solid
electrolyte membrane.
30. The fuel cell of claim 29 further comprising gas diffusion
backings adjacent the anode and cathode.
31. The fuel cell of claim 28 further comprising gas diffusion
electrodes comprising a gas diffusion backing and an electrode
present on the first and second surfaces of the solid polymer
electrolyte membrane, wherein the electrode is adjacent the solid
polymer electrolyte membrane.
32. The fuel cell of claim 29 further comprising a means for
delivering fuel to the anode, a means for delivering oxygen to the
cathode, a means for connecting the anode and cathode to an
external electrical load, methanol in the liquid or gaseous state
in contact with the anode, and oxygen in contact with the
cathode.
33. The fuel cell of claim 28 wherein the fuel is hydrogen.
34. The fuel cell of claim 28 wherein the fuel is an alcohol.
35. The fuel cell of claim 34 wherein the fuel is methanol.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a novel compound and its
use in electrochemical cells as an electrolyte, and more
particularly to the use of the compound in fuel cells.
BACKGROUND OF THE INVENTION
[0002] Electrochemical cells, such as fuel cells and lithium-ion
batteries are known. Depending on the operating conditions, each
type of cell places a particular set of requirements upon the
electrolytes used in them. For fuel cells, this is typically
dictated by the type of fuel, such as hydrogen or methanol, used to
power the cell and the composition of the membrane used to separate
the electrodes. Proton-exchange membrane fuel cells, powered by
hydrogen as the fuel, could be run at higher operating temperatures
than currently employed to take advantage of lower purity feed
streams, improved electrode kinetics, better heat transfer from the
fuel cell stack to improve its cooling. Waste heat is also employed
in a useful fashion. However, if current fuel cells are to be
operated at greater than 100.degree. C. then they must be
pressurized to maintain adequate hydration of typical
proton-exchange membranes, such as DuPont Nafion.RTM.
perfluorosulfonic acid membrane, to support useful levels of proton
conductivity.
[0003] There is an ongoing need to discover novel electrolytes that
improve the performance of the latest generation of electrochemical
cells, such as fuel cells and lithium-ion batteries, and form
membrane materials that maintain adequate proton conductivity at
lower levels of hydration.
SUMMARY OF THE INVENTION
[0004] In a first aspect, the invention provides a compound having
the following structure:
Zr(O.sub.3PZ.sub.qY.sub.nX).sub.2-m(O.sub.3PR).sub.m wherein X=a
functional group selected from the group consisting of CO.sub.2H,
PO(OH).sub.2, SO.sub.3H, and SO.sub.2NHSO.sub.2W, wherein W=aryl of
6 to 10 carbon atoms or Y; Y=perfluoro-linear, branched or cyclic
alkylene group, wherein the alkylene is 1-20 carbon atoms, or a
fluorinated group containing at least one substituent selected from
the group consisting of oxygen, chlorine and bromine; Z=alkylene of
1-12 carbon atoms, aryl of 6-10 carbon atoms, or a heterocyclic
aryl group of 3-10 carbons atoms; R=alkyl of 1-12 carbon atoms,
aryl of 6-10 carbon atoms, substituted alkyl, or substituted aryl,
wherein the substituent is selected from the group consisting of F,
Cl, perfluoroalkyl, alkyl of 1-12 carbon atoms and aryl of 6-10
carbon atoms; n=0 or 1; q=0 or 1; and m=0 to 1.5; with the proviso
that when n=0, and q=1, Z=at least one heterocyclic group having 3
to 10 carbon atoms, 1 to 5 nitrogen atoms and 0 to 4 oxygen
atoms.
[0005] In a second aspect, the invention provides a functionalized
phosphonic acid having the following structure:
(HO).sub.2OPZ.sub.qY.sub.nX. wherein X=a functional group selected
from the group consisting of CO.sub.2H, PO(OH).sub.2, SO.sub.3H,
and SO.sub.2NHSO.sub.2W, wherein W=aryl of 6 to 10 carbon atoms or
Y; Y=perfluoro-linear, branched or cyclic alkylene group, wherein
the alkylene is 1-20 carbon atoms, or a fluorinated group
containing at least one substituent selected from the group
consisting of oxygen, chlorine and bromine; Z=alkylene of 1-12
carbon atoms, aryl of 6-10 carbon atoms, or a heterocyclic aryl
group of 3-10 carbons atoms; n=0 or 1; and q=0 or 1; with the
proviso that when n=0, and q=1, Z=at least one heterocyclic group
having 3 to 10 carbon atoms, 1 to 5 nitrogen atoms and 0 to 4
oxygen atoms.
[0006] In a third aspect, the invention provides a solid
electrolyte membrane comprising a compound having the following
structure: Zr(O.sub.3PZ.sub.qY.sub.nX).sub.2-m(O.sub.3PR).sub.m
wherein X=a functional group selected from the group consisting of
CO.sub.2H, PO(OH).sub.2, SO.sub.3H, and SO.sub.2NHSO.sub.2W,
wherein W=aryl of 6 to 10 carbon atoms or Y; Y=perfluoro-linear,
branched or cyclic alkylene group, wherein the alkylene is 1-20
carbon atoms, or a fluorinated group containing at least one
substituent selected from the group consisting of oxygen, chlorine
and bromine; Z=alkylene of 1-12 carbon atoms, aryl of 6-10 carbon
atoms, or a heterocyclic aryl group of 3-10 carbons atoms; R=alkyl
of 1-12 carbon atoms, aryl of 6-10 carbon atoms, substituted alkyl,
or substituted aryl, wherein the substituent is selected from the
group consisting of F, Cl, perfluoroalkyl, alkyl of 1-12 carbon
atoms and aryl of 6-10 carbon atoms; n=0 or 1; q=0 or 1; and m=0 to
1.5; with the proviso that when n=0, and q=1, Z=at least one
heterocyclic group having 3 to 10 carbon atoms, 1 to 5 nitrogen
atoms and 0 to 4 oxygen atoms. These membranes are particularly
useful at temperatures of at least 100.degree. C. Typically the
compound is imbibed into a porous support to form the solid polymer
electrolyte membrane.
[0007] In a fourth aspect, the invention provides a catalyst coated
membrane comprising a solid electrolyte membrane having a first
surface and a second surface, an anode present on the first surface
of the solid electrolyte membrane, and a cathode present on the
second surface of the solid electrolyte membrane, wherein the solid
electrolyte membrane comprises a compound having the following
structure: Zr(O.sub.3PZ.sub.qY.sub.nX).sub.2-m(O.sub.3PR).sub.m
wherein X=a functional group selected from the group consisting of
CO.sub.2H, PO(OH).sub.2, SO.sub.3H, AND SO.sub.2NHSO.sub.2W,
wherein W=aryl of 6 to 10 carbon atoms or Y; Y=perfluoro-linear,
branched or cyclic alkylene group, wherein the alkylene is 1-20
carbon atoms, or a fluorinated group containing at least one
substituent selected from the group consisting of oxygen, chlorine
and bromine; Z=alkylene of 1-12 carbon atoms, aryl of 6-10 carbon
atoms, or a heterocyclic aryl group of 3-10 carbons atoms; R=alkyl
of 1-12 carbon atoms, aryl of 6-10 carbon atoms, substituted alkyl,
or substituted aryl, wherein the substituent is selected from the
group consisting of F, Cl, perfluoroalkyl, alkyl of 1-12 carbon
atoms and aryl of 6-10 carbon atoms; n=0 or 1; q=0 or 1; and m=0 to
1.5; with the proviso that when n=0, and q=1, Z=at least one
heterocyclic group having 3 to 10 carbon atoms, 1 to 5 nitrogen
atoms and 0 to 4 oxygen atoms. The compound may be introduced into
the membrane by various methods, e.g. by imbibing into a porous
support.
[0008] In a fifth aspect, the invention provides a fuel cell
comprising a solid electrolyte membrane having a first surface and
a second surface, wherein the solid electrolyte membrane comprises
a compound having the following structure:
Zr(O.sub.3PZ.sub.qY.sub.nX).sub.2-m(O.sub.3PR).sub.m wherein X=a
functional group selected from the group consisting of CO.sub.2H,
PO(OH).sub.2, SO.sub.3H, and SO.sub.2NHSO.sub.2W, wherein W=aryl of
6 to 10 carbon atoms or Y; Y=perfluoro-linear, branched or cyclic
alkylene group, wherein the alkylene is 1-20 carbon atoms, or a
fluorinated group containing at least one substituent selected from
the group consisting of oxygen, chlorine and bromine; Z=alkylene of
1-12 carbon atoms, aryl of 6-10 carbon atoms, or a heterocyclic
aryl group of 3-10 carbons atoms; R=alkyl of 1-12 carbon atoms,
aryl of 6-10 carbon atoms, substituted alkyl, or substituted aryl,
wherein the substituent is selected from the group consisting of F,
Cl, perfluoroalkyl, alkyl of 1-12 carbon atoms and aryl of 6-10
carbon atoms; n=0 or 1; q=0 or 1; and m=0 to 1.5; with the proviso
that when n=0, and q=1, Z=at least one heterocyclic group having 3
to 10 carbon atoms, 1 to 5 nitrogen atoms and 0 to 4 oxygen
atoms.
[0009] In the fifth aspect, the fuel cell further comprises an
anode and a cathode present on the first and second surfaces of the
electrolyte membrane. Gas diffusion backings may be present on the
side of the anode or cathode away from the solid polymer
electrolyte membrane. Alternately, gas diffusion electrodes
comprising a gas diffusion backing and an electrode may be present
on the first and second surfaces of the solid polymer electrolyte
membrane, wherein the electrode is adjacent the solid polymer
electrolyte membrane.
[0010] In the fifth aspect, the fuel cell further comprises a means
for delivering fuel to the anode, a means for delivering oxygen to
the cathode, a means for connecting the anode and cathode to an
external electrical load, methanol in the liquid or gaseous state
in contact with the anode, and oxygen in contact with the cathode.
The fuel is in the liquid or vapor phase. Some suitable fuels
include hydrogen, and alcohols such as methanol and ethanol,
etc.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a schematic illustration of a single cell
assembly.
DETAILED DESCRIPTION OF THE INVENTION
[0012] The compounds of the invention that may be small molecules
are useful as electrolytes in the preparation of the solid
electrolyte membranes. These solid electrolyte membranes may be
used to make catalyst coated membranes that are a component of fuel
cells.
Compound:
[0013] The compound of the invention has the following structure:
Zr(O.sub.3PZ.sub.qY.sub.nX).sub.2-m(O.sub.3PR).sub.m wherein X=a
functional group selected from the group consisting of CO.sub.2H,
PO(OH).sub.2, SO.sub.3H, AND SO.sub.2NHSO.sub.2W; wherein W=aryl of
6 to 10 carbon atoms or --Y; Y=perfluoro-linear, branched or cyclic
alkylene group, wherein the alkylene is 1-20 carbon atoms such as
perfluoromethylene, perfluoroethylene, perfluoropropylene or a
fluorinated group containing at least one substituent selected from
the group consisting of oxygen, chlorine and bromine selected from
the group consisting of CF.sub.2CF.sub.2OCF.sub.2CF.sub.2 or
CF.sub.2CFCF.sub.3OCF.sub.2CF.sub.2; Z=alkylene of 1-12 carbon
atoms such as methylene, ethylene and propylene, aryl of 6-10
carbon atoms such as phenyl, or substituted phenyl, wherein the
substituent is selected from the group consisting of, F, Cl,
perfluoroalkyl such as trifluoromethyl, pentafluoroethyl, alkyl of
1-12 carbon atoms such as methyl, ethyl, propyl, butyl;
naphthalene; or a heterocyclic aryl group of 3-10 carbons atoms
such as benzimidazole, imidazole, pyrazole, triazole, thiazole, or
oxadiazole; R=alkyl of 1-12 carbon atoms such as methylene,
ethylene and propylene; aryl of 6-12 carbon atoms such as benzene,
or substituted benzene, naphthalene or substituted naphthalene;
wherein the substituent is selected from the group consisting of F,
Cl, perfluoroalkyl such as trifluoromethyl, pentafluoroethyl, alkyl
of 1-12 carbon atoms such as methyl, ethyl, propyl, butyl, more
typically methyl, and aryl of 6-12 carbon atoms such as benzene, or
substituted benzene, wherein the substituent is selected from the
group consisting of F, Cl, perfluoroalkyl such as trifluoromethyl,
pentafluoroethyl, and alkyl of 1-12 carbon atoms such as methyl,
ethyl, propyl, butyl; n=0 or 1; q=0 or 1; m=0 to 1.5; and with the
proviso that when n=0, and q=1, Z=heterocyclic groups having 3 to
12 carbon atoms such as benzimidazole, imidazole, pyrazole,
triazole, thiazole, or oxadiazole; more typically 3 to 8 carbon
atoms, 1 to 5 nitrogen atoms, more typically 2 to 3 nitrogen atoms,
and 0 to 4 oxygen atoms, more typically 0 to 2 oxygen atoms.
[0014] Some suitable heterocyclic groups include, benzimidazole,
imidazole or oxadiazole. Some suitable compounds include
Zr(HO.sub.2CCF.sub.2CH.sub.2CH.sub.2CH.sub.2PO.sub.3).sub.2,
Zr(H.sub.2O.sub.3PCF.sub.2CH.sub.2CH.sub.2CH.sub.2PO.sub.3).sub.2,
Zr(HO.sub.3SCF.sub.2CF.sub.2OCF.sub.2CF.sub.2CH.sub.2CH.sub.2CH.sub.2PO.s-
ub.3).sub.2, Zirconium(2-benzimidazolyl-2-ethylphosphonate),
Zirconium(2-imidazolyl-2-ethylphosphonate),
Zirconium(2-pyrazolyl-2-ethylphosphonate),
Zirconium(2-oxadiazolyl-2-ethylphosphonate)
[0015] The compound may be prepared by several reaction steps from
iodo substituted perfluoroalkylene functionalized compounds such as
IR.sub.FX', where R.sub.F is perfluoro-linear, branched or cyclic
alkylene group, wherein the alkylene is 1-20 carbon atoms such as
perfluoromethylene, perfluoroethylene or a fluorinated group
containing substituents selected from the group consisting of
oxygen, chlorine and bromine such as
CF.sub.2CF.sub.2OCF.sub.2CF.sub.2,
CF.sub.2CFCF.sub.3OCF.sub.2CF.sub.2, and X' is a precursor group
such as SO.sub.2F, PO(OEt).sub.2 or CO.sub.2Et of functionalized
groups X, such as SO.sub.3H, SO.sub.2NSO.sub.2CF.sub.3,
PO(OH).sub.2, CO.sub.2H. Addition of IR.sub.FX' to
alkenylphosphonates such as diethyl allylphosphonate gives the
corresponding adducts with a radical initiator such as benzoyl
peroxide or metals such as Cu and Pd(PPh.sub.3).sub.4 or salts such
as Na.sub.2S.sub.2O.sub.4. Adducts were reduced to remove iodine
with a reducing reagent such as Bu.sub.3SnH, Zn/HCl, Zn/NiCl.sub.2
and so on. Finally, hydrolysis of the phosphonate with aqueous acid
such as aqueous HCl produced the corresponding phosphonic acid,
which reacted with ZrOCl.sub.2 in acidic water to give a compound
Zr[O.sub.2POR'CH.sub.2CH.sub.2R.sub.FX].sub.2.
[0016] In the presence of other phosphonic acids, the mixed
Zirconium phosphonate was formed as shown by this reaction:
##STR1##
[0017] Alternatively, functionalized phosphonic acid may be
directly reacted with ZrOCl.sub.2 in acidic water. This is
particularly used for the production of Zr phosphonate containing
heterocyclic ring structures such as benzimidazole, imidazole,
pyrazole, triazole, thiazole, or oxadiazole; A typical example
includes the following: ##STR2## Membrane:
[0018] The compound identified above is useful in forming a solid
electrolyte membrane, typically capable of operating at a
temperature of at least 100.degree. C. In a first method, the
electrolyte may be directly pressed into thin films or a mixture of
the electrolyte with other thermally and chemically stable polymers
may be pressed into a film.
[0019] In a second method the electrolyte may be ground to a fine
powder, and then dispersed in polymeric solution such as
polyvinylidene fluoride in organic solvent. The dispersion may then
be cast into a thin film on a glass plate and baked to remove
solvent.
[0020] In a third method a mixture of the electrolyte and
optionally a crosslinkable monomer may be poured into a porous
support followed by drying, with or without heat, to insure that
the electrolyte stayed in the porous structure.
[0021] The porous support of the membrane may be made from a wide
range of components. Some examples include porous supports made
from hydrocarbons such as a polyolefin, e.g., polyethylene,
polypropylene, polybutylene, copolymers of those materials, and the
like. Perhalogenated polymers such as polychlorotrifluoroethylene
may also be used. For resistance to thermal and chemical
degradation, the support typically is made of a highly fluorinated
polymer, most preferably perfluorinated polymer.
[0022] For example, the polymer for the porous support can be a
microporous film of polytetrafluoroethylene (PTFE) or a copolymer
of tetrafluoroethylene with other perfluoroalkyl olefins or with
perfluorovinyl ethers. Microporous PTFE films and sheeting are
known which are suitable for use as a support layer. For example,
U.S. Pat. No. 3,664,915 discloses uniaxially stretched film having
at least 40% voids. U.S. Pat. Nos. 3,953,566, 3,962,153 and
4,187,390 disclose porous PTFE films having at least 70% voids.
[0023] Alternatively, the porous support may be a fabric made from
fibers of the support polymers discussed above woven using various
weaves such as the plain weave, basket weave, leno weave, or
others. A membrane suitable for the practice of the invention can
be made by coating the porous support fabric with the compound,
also known as the electrolyte, of the invention to form a composite
membrane. To be effective the coating should typically be on both
the outside surfaces as well as distributed through the internal
pores of the support. This may be accomplished by impregnating the
porous support with a solution or dispersion of the solid
electrolyte, using a solvent that is not harmful to the compound or
the support, and under impregnation conditions that provide
improved imbibing of the compound solution or dispersion into the
support. This results in a thin, even coating of the compound on
the support. The support with the solution/dispersion is dried with
or without heat to form the membrane. If desired, thin films of the
solid electrolytes can be laminated to one or both sides of
impregnated porous support to prevent bulk flow through the
membrane that can occur if large pores remain in the membrane after
impregnation. It is preferred for the compound to be present as a
continuous phase within the membrane.
[0024] In a fourth method the solid electrolyte may be imbibed
in-situ into inorganic materials such as glass paper. The glass or
other porous membranes first absorb aqueous ZrOCl.sub.2 solution,
and may then be immersed in a solution of
(HO).sub.2OPZ.sub.qY.sub.nX to form a supporting membrane
containing the electrolyte.
Fuel Cell:
[0025] As shown in FIG. 1, the fuel cell comprises a catalyst
coated membrane (CCM) (10) in combination with at least one gas
diffusion backing (GDB) (13) to form an unconsolidated membrane
electrode assembly (MEA). The catalyst coated membrane (10)
comprises an ion exchange polymer membrane (11) discussed above and
catalyst layers or electrodes (12) formed from a electrocatalyst
coating composition. The fuel cell is further provided with an
inlet (14) for fuel, such as liquid or gaseous alcohols, e.g.
methanol and ethanol, or hydrogen; an anode outlet (15); a cathode
gas inlet (16); a cathode gas outlet (17); aluminum end blocks (18)
tied together with tie rods (not shown); a gasket for sealing (19);
an electrically insulating layer (20); graphite current collector
blocks with flow fields for gas distribution (21); and gold plated
current collectors (22).
[0026] The fuel cell utilizes a fuel source that may be in the
liquid or gaseous phase, and may comprise hydrogen, or an alcohol.
Typically a methanol/water solution is supplied to the anode
compartment and air or oxygen supplied to the cathode
compartment.
Catalyst Coated Membrane (CCM):
[0027] A variety of techniques are known for CCM manufacture which
apply an electrocatalyst coating composition similar to that
described above onto the solid fluorinated polymer electrolyte
membrane. Some known methods include spraying, painting, patch
coating and screen, decal, pad or flexographic printing.
[0028] In one embodiment of the invention, the MEA (30), shown in
FIG. 1, may be prepared by thermally consolidating the gas
diffusion backing (GDB) with a CCM at a temperature of under
200.degree. C., preferably 140-160.degree. C. The CCM may be made
of any type known in the art. In this embodiment, an MEA comprises
a solid electrolyte (SPE) membrane with a thin catalyst-binder
layer disposed thereon. The catalyst may be supported (typically on
carbon) or unsupported. In one method of preparation, a catalyst
film is prepared as a decal by spreading the catalyst ink on a flat
release substrate such as Kapton.RTM. polyimide film (available
from the DuPont Company). After the ink dries, the decal is
transferred to the surface of the SPE membrane by the application
of pressure and heat, followed by removal of the release substrate
to form a catalyst coated membrane (CCM) with a catalyst layer
having a controlled thickness and catalyst distribution.
Alternatively, the catalyst layer is applied directly to the
membrane, such as by printing, and then the catalyst film is dried
at a temperature not greater than 200.degree. C.
[0029] The CCM, thus formed, is then combined with a GDB to form
the MEA (30). The MEA is formed, by layering the CCM and the GDB,
followed by consolidating the entire structure in a single step by
heating to a temperature no greater than 200.degree. C., preferably
in the range of 140-160.degree. C., and applying pressure. Both
sides of the MEA can be formed in the same manner and
simultaneously. Also, the composition of the catalyst layer and GDB
could be different on opposite sides of the membrane.
[0030] The invention is further illustrated by the following
examples.
EXAMPLES
Method of Measuring Through-Plane, High-Temperature, No-Water-Added
Membrane Conductivity:
[0031] The conductivity of the pellets or films was measured by a
technique in which the current flows through (perpendicular to) the
plane of the pellet or films. A lower electrode was formed from a
12.7 mm diameter stainless steel rod and an upper electrode was
formed from a 6.35 mm diameter stainless steel rod. The rods were
cut to length, their ends polished, and then they were gold plated.
A stack was formed consisting of lower electrode/GDE/film/GDE/upper
electrode. The GDE (gas diffusion electrode) was obtained from
DeNora E-TEK, Somerset, N.J., and was a catalyzed ELAT.RTM.
comprising carbon cloth, a microporous layer, Pt catalyst, and a
0.6-0.8 mg/cm.sup.2 Nafion.RTM. application over the catalyst
layer. The lower GDE was punched out as a 9.5 mm diameter disk,
while the film and the upper GDE were punched out as 6.35 mm
diameter disks to match the upper electrode. The stack was
assembled and held in place in a block of machinable glass ceramic
(Corning MACOR.RTM.) that had a 12.7 mm diameter hole drilled into
the bottom of the block, that accepted the lower electrode. A
concentric 6.4 mm diameter hole was drilled into the top of the
block, that accepted the upper electrode. A force of 270 N was
applied to the stack by means of a clamp and calibrated spring.
This produced a pressure of 8.6 MPa in the active area under the
upper electrode, insuring low impedance ionic contact of the GDE's
to the film. The fixture was placed in an oven for measurements at
temperatures of 25.degree. C. to 180.degree. C. The real part of
the AC impedance of the fixture containing the sample film was
measured at a frequency of 100 kHz (R.sub.s) using a
potentiostat/frequency response analyzer (PC4/750.TM. potentiostat
with EIS software), (Gamry Instruments, Warminster, Pa.). The
fixture short (R.sub.f) was also determined by measuring the real
part of the 100 kHz AC impedance of the fixture assembled with the
stack and both GDE's, but without the film. The conductivity was
calculated as .kappa.=t/((R.sub.s-R.sub.f).times.0.317 cm.sup.2),
where t was the thickness of the pellets or films in cm. Method of
Measuring In-Plane Membrane Conductivity:
[0032] The membrane sample was loaded on a four point conductivity
probe. The probe has a base plate that measures
1.9''.times.1.5''.times.0.385'' and a cover plate
1.9''.times.1.23''.times.0.25''. Four 0.5'' long platinum wires (30
GA, Hauser and Miller Precious Metals) were fixed on top of four
0.05'' wide ridges along the width direction of the base plate. The
outer two probes has a spacing of 1'' and the inner two probes has
a spacing of 0.4''. In between the ridges, the space was open so
that the membrane was exposed to the environment. The membrane
sample, typically 1 cm wide and 3.25 cm long was pressed against
the four platinum probes with the cover plate by a clamp. The
membrane was also exposed to the environment on the cover plate
side, which also had the openings. The four platinum wires were
connected electrically to a Solatron.RTM. impedance measurement
system consisting of a SI1287 electrochemical interface and a 1255B
frequency response analyzer. To measure the membrane conductivity,
the probe was dipped into a 500 mL glass beaker filled with the
desired solution so that the membrane was fully exposed to the
solution. The glass beaker was wrapped with heating tape, which was
connected to a digital thermal controller. The thermocouple of the
controller was immersed in the solution so that the solution
temperature was precisely controlled.
[0033] Since the solution itself may have finite conductivity, it
was important to correct for that in the measurement. This was
accomplished by measuring separately the resistances of the cell
when the membrane sample was loaded (R) and when a thin Teflon.RTM.
film was loaded (R.sub.0). The resistance (R.sub.s) due to the
sample was then calculated by the formula:
Rs=R.times.R.sub.0/(R.sub.0-R). The sample membrane conductivity
was then calculated by the formula: .sigma.=L/(Rs.times.A) where
.sigma. was conductivity (S/cm), L (cm) was the spacing between the
inner two wires and A (cm.sup.2) was the cross sectional area of
the membrane.
Example 1
[0034] (EtO).sub.2POCH.sub.2CH.sub.2CH.sub.2CF.sub.2CO.sub.2Et was
prepared using the following procedure:
[0035] A flask was charged with 4.0 g of NiCl.sub.2/6H.sub.2O, 13.0
g of Zn powder, 200 mL of THF and 3 mL of water. The resulting
mixture was stirred at room temperature for 30 min, 35.0 g of
diethyl allylphosphonate and 50.0 g of ICF.sub.2CO.sub.2Et were
added, the mixture was stirred at room temperature overnight, and
then poured into aqueous NH.sub.4Cl solution. Solid was removed by
filtration and the filtrate was extracted with ether (300
mL.times.3). The combined ether layers were washed with water,
dried over MgSO.sub.4. After removal of the ether, the residue was
distilled to give 19.4 g of the title product, bp 113.degree. C./5
mmHg. .sup.1H NMR: 4.25 (q, J=7 Hz, 2H), 4.01 (m, 4H), 2.10 (m,
2H), 2.75 (m, 4H), 1.30 (m, 9H). .sup.19F NMR: -105.6 (m). HRMS:
Calcd. for C.sub.11H.sub.21O.sub.5F.sub.2P.sub.1: 303.1173. Found:
303.1169.
[0036] (EtO).sub.2POCH.sub.2CH.sub.2CH.sub.2CF.sub.2CO.sub.2Et was
used to prepare
(HO).sub.2POCH.sub.2CH.sub.2CH.sub.2CF.sub.2CO.sub.2H using the
following procedure:
[0037] A mixture of 19.0 g of
(EtO).sub.2POCH.sub.2CH.sub.2CH.sub.2CF.sub.2CO.sub.2Et and 50 mL
of conc. HCl was refluxed for 7 days. After removal of all
volatiles, the residue was dried under vacuum to give 11.8 g of the
title compound.
[0038] A glass tube was charged with the title compound and water
in a ratio of 85 to 1 by weight. A liquid conductivity probe was
inserted into the tube and the unsealed tube was mounted in a
controlled-temperature oven. The AC impedance was measured at 1 kHz
as the tube was twice heated to 150.degree. C. and cooled in
25.degree. C. steps. The following conductivities were calculated
using a cell constant for the probe measured using a NIST traceable
conductivity calibration standard for 0.1 siemens. The sample has
conductivity of 129 mS/cm at 80.degree. C. and 4.69 mS/cm at
120.degree. C.
[0039] (HO).sub.2POCH.sub.2CH.sub.2CH.sub.2CF.sub.2CO.sub.2H was
used to prepare
Zr(O.sub.3PCH.sub.2CH.sub.2CH.sub.2CF.sub.2CO.sub.2H).sub.2 using
the following procedure:
[0040] 1.6 g (5 mmol) of ZrOCl.sub.2/8H.sub.2O was dissolved in 30
mL of water and 4.5 mL of 50% HF and then poured in to a solution
of 2.18 g (10 mmol) of
(HO).sub.2OPCH.sub.2CH.sub.2CH.sub.2CF.sub.2CO.sub.2H in 20 mL of
water. After being stirred at 70-80.degree. C. for 3 days and at
room temperature for 16 hrs, the resulting mixture was transferred
into a glass tube and centrifuged. Solids were separated and washed
with water thrice, and dried in a vacuum oven at 90.degree. C. to
give 2.3 g of
Zr(O.sub.3PCH.sub.2CH.sub.2CH.sub.2CF.sub.2CO.sub.2H).sub.2. The
pellet (0.3 cm diameter in size) was pressed at room temperature
and conductivity, measured using the procedure described above, was
found to be 0.01 mS/cm at 150.degree. C.
Example 2
[0041] (HO).sub.2OPCH.sub.2CH.sub.2CH.sub.2CF.sub.2PO(OH).sub.2 was
prepared using the following procedure:
[0042] A mixture of 28.51 g of diethyl allylphosphonate, 47.1 g of
ICF.sub.2PO(OEt).sub.2, 0.98 g of Cu powder in 120 mL of CH.sub.3CN
was stirred at 80.degree. C. for 8 hours. After removal of
volatiles, the residue was diluted with ether, filtered, evaporated
to give 61.0 g of
(EtO).sub.2OPCH.sub.2CHICH.sub.2CF.sub.2PO(OEt).sub.2. HRMS: calcd.
for C.sub.11H.sub.21O.sub.5F.sub.2P.sub.1: 303.11729. Found:
303.11686.
[0043] A flask was charged with 0.24 g of NiCl.sub.2/6H.sub.2O, 2.0
g of Zn powder, 100 mL of THF and 0.5 mL of water. The resulting
mixture was stirred at room temperature for 20 min. 9.2 g of
(EtO).sub.2OPCH.sub.2CHICH.sub.2CF.sub.2PO(OEt).sub.2 were added
and the mixture was stirred at room temperature overnight and then
filtered. The filtrate was evaporated and the residue was diluted
with ether, washed with aqueous NH.sub.4Cl solution, water and
dried over MgSO.sub.4. After removal, 3.95 g of the ether,
(EtO).sub.2OPCH.sub.2CH.sub.2CH.sub.2CF.sub.2PO(OEt).sub.2, were
obtained. A mixture of 3.95 g of
(EtO).sub.2OPCH.sub.2CH.sub.2CH.sub.2CF.sub.2PO(OEt).sub.2 and 40
mL of conc. HCl was refluxed for 2 days, and then evaporated and
dried to give 2.8 g of product. .sup.19F NMR: -112.9 (dt, J=102 Hz,
J=18.8 Hz). .sup.1H NMR: 2.1(m, 2H), 1.70 (m, 4H).
[0044]
Zr[O.sub.3PCH.sub.2CH.sub.2CH.sub.2CF.sub.2PO(OH).sub.2].sub.2 was
prepared using the following procedure:
[0045] 0.71 g (2.2 mmol) of ZrOCl.sub.2/6H.sub.2O was dissolved in
8 mL of water and 1.0 mL of 50% HF and then poured into a solution
of 1.1 g (4.3 mmol) of
(HO).sub.2OPCH.sub.2CH.sub.2CH.sub.2CF.sub.2PO(OH).sub.2 in 17 mL
of water. After being stirred at 70-80.degree. C. f, or 20 hr, and
at room temperature for 24 hr, the resulting mixture was
transferred into a glass tube and centrifuged. Solids were
separated and washed with water thrice, and dried in a vacuum oven
at 100.degree. C. to give 0.71 g of
Zr[O.sub.3PCH.sub.2CH.sub.2CH.sub.2CF.sub.2PO(OH).sub.2].sub.2.
[0046] The pellet was pressed at room temperature and conductivity
(through plane) at 125.degree. C., measured using the procedure
described above, was found to be 27.98 mS/cm.
Example 3
(EtO).sub.2OPCH.sub.2CH.sub.2CH.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2SO-
.sub.2F was prepared using the following procedure:
[0047] A mixture of 110.6 g of diethyl allylphosphonate, 277.6 g of
ICF.sub.2CF.sub.2OCF.sub.2CF.sub.2SO.sub.2F was heated to 80 to
85.degree. C. under N.sub.2. 0.5 g of benzoyl peroxide was added
and the reaction mixture was stirred for 1.5 hr. Additional 0.5 g
of benzoyl peroxide was added and the mixture was stirred for 2 hr
and these steps were repeated four more times. GC indicated no
starting materials. The mixture was evaporated to remove excess
diethyl allylphosphonate. 120 mL of Bu.sub.3SnH were added and the
mixture was stirred until no starting material remained. It was
then diluted with ether, and treated with aqueous KF solution to
remove Bu.sub.3SnI, washed with water and dried over MgSO.sub.4.
After removal of the ether, 159.3 g of product were obtained.
.sup.19F NMR: +44.4 (s, 1F), -83.7 (m, 2F), -88.9 (m, 2F),
-113.2(s, 2F), -118.8 (m, 2F). HRMS: Calcd for
C.sub.11H.sub.16O.sub.6F.sub.9P.sub.11S: 479.03398: Found:
479.03253.
[0048]
(HO).sub.2OPCH.sub.2CH.sub.2CH.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.su-
b.2SO.sub.2F was prepared using the following procedure:
[0049] A mixture of 46.9 g of
(EtO).sub.2OPCH.sub.2CH.sub.2CH.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2SO.-
sub.2F and conc. 200 mL of concentrated HCl was heated at
110.degree. C. for 4 days and evaporated to remove volatile to give
product. .sup.19F NMR: +44.7 (s, 1F), -83.3 (m, 2F), -87.7 (m, 2F),
-112.9 (s, 2F), -118.3 (m, 2F).
[0050]
(HO).sub.2OPCH.sub.2CH.sub.2CH.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.su-
b.2SO.sub.3H was prepared using the following procedure:
[0051] A mixture of 10.0 g of
(EtO).sub.2OPCH.sub.2CH.sub.2CH.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2SO.-
sub.2F and 2.5 g of LiOH in 60 mL of MeOH was stirred overnight and
then filtered and evaporated to give solids, which were boiled with
dry CH.sub.3CN (3.times.60 mL), filtered and the filtrates were
evaporated to give 10.1 g of product. .sup.19F NMR indicated no
sulfonyl fluoride peak. The solids were refluxed with 80 mL of
conc. HCl for 2 days. After removal of volatiles, 8.2 grams of
residue were obtained. .sup.19F NMR: -82.9 (m, 2F), -88.5 (s, 2F),
-118.0 (m, 2F), -118.5 (s, 2F). 7.2 g of solids were dissolved in
water and run through an ion exchange column at two drops per
minute and then evaporated and dried at 100.degree. C. in full
vacuum to give 6.65 g of wax solids.
[0052]
Zr[O.sub.3PCH.sub.2CH.sub.2CH.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub-
.2SO.sub.3H].sub.2 was prepared using the following procedure:
[0053] 0.39 g (1.2 mmol) of ZrOCl.sub.2/8H.sub.2O was dissolved in
5 mL of water and then poured in to a solution of 1.0 g (2.38 mmol)
of
(HO).sub.2OPCH.sub.2CH.sub.2CH.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2SO.s-
ub.3H in 5 mL of water. After being stirred at 70-80.degree. C. for
20 hours, the mixture was then heated in a vacuum oven at
85.degree. C. for 54 hrs and at 110.degree. C. for 6 hrs. 1.03 g of
brown solid were obtained, that were ground into a fine powder, and
pressed into pellets. Conductivity, measured using the procedure
described above, was found to be 15.10 mS/cm at 150.degree. C.
Example 4
[0054] Benzimidazolyl-2-ethylenephosphonic acid was prepared using
the following procedure:
[0055] A mixture of 10.8 g (0.1 mol) of 20.6 mL (0.093 mol), 41.7 g
of concentration HCl and 41.7 g of water was refluxed 15 hr and
then neutralized with 50% NaOH to pH=14. The reaction mixture was
extracted with CH.sub.2Cl.sub.2 (3.times.100 mL) and aqueous layer
comprised of (sodium benzimidazolyl-2-ethylenephosphonate) was
treated with concentrated HCl to pH=5. Solids were filtered, washed
with water for five times, dried in air and then in a vacuum oven
at 60.degree. C. for 24 hr to give 15.6 g of product.
[0056] Zr(benzimidazolyl-2-ethylenephosphonate) was prepared using
the following procedure:
[0057] A solution of 1.5 g of benzimidazolyl-2-ethylenephosphonic
acid in 35 mL of water and 7 mL of con. HCl was poured into a
solution of 0.806 g (2.5 mmol) of ZrOCl26H2O. The resulting mixture
was stirred at 80.degree. C. for 16 hrs and at room temperature for
48 hrs. After removal of the liquid, the solid was washed with
aqueous NaOH to a pH=8, and then washed with water and dried in a
vacuum oven to give 1.5 g of powder. This was pressed to a pellet
with thickness of 0.885 mm. Conductivity, measured using a
through-plane high temperature conductivity measurement technique
described above, was 1.45 mS/cm at 100.degree. C. and 2.30 mS/cm at
125.degree. C.
[0058] Zr(benzimidazolyl-2-ethylenephosphonate) in the presence of
HF was prepared using the following procedure:
[0059] A solution of 4.5 g of benzimidazolyl-2-ethylenephosphonic
acid in 50 mL of water and 12 mL of conc. HCl was poured into a
solution of 3.22 g (10.0 mmol) of ZrOCl.sub.2/6H.sub.2O, 5.1 mL of
51% HF and 20 mL of water. The resulting mixture was stirred at
80.degree. C. for 18 hrs and at room temperature for 24 hr, and
then transferred into a glass tube and centrifuged. After removal
of the top layer, the white solid was dried in a vacuum oven at
90.degree. C. for 24 hr and suspended in EtOH. The suspension was
neutralized with 10% KOH solution to pH=8.5. The solid was
collected after centrifugation, washed with water and dried in the
vacuum oven at 90.degree. C. to give 1.93 g of white solid, that
was pressed into a pellet with a thickness of 0.887 mm.
Conductivity, measured using the procedure described above, was
found to be 1.80 mS/cm at 100.degree. C.
Example 5
[0060] This example used a modified ceramic fiber sheet, product #
ASPA-1, from ZIRCAR ceramics, Inc., Florida, N.Y. The sheet
nominally contained 51 wt % silica, 45 wt % alumina, and 4%
hydrocarbon binder. The original binder was burned off in an
800.degree. C. furnace for 4 hours. The sheet was then saturated
with a 2% solution of Kynar.RTM. 741 PVDF resin (Atofina Chemicals,
Inc., Philadephia, Pa.) in dimethylacetamide, allowed to sit for 5
minutes, and dried in a vacuum oven at 110.degree. C. for 1 hour.
The sheet was immersed in a solution of 2.6 g of ZrOCl.sub.2 and 25
mL of water at room temperature overnight. The film was transferred
into a solution of 1.5 g of
(HO).sub.2POCH.sub.2CH.sub.2CH.sub.2CF.sub.2CO.sub.2H in 20 mL of
water at 85.degree. C. for 8 hr and at held at room temperature for
2 days. The film was removed and washed with de-ionized water 5
times and dried in a vacuum oven at 100.degree. C. overnight to
give a membrane weighing 0.760 g (137% weight increase).
[0061] The membrane was loaded in an in-plane conductivity test
cell containing a four-point probe as described above. The probe
fixture placed four parallel platinum wires in contact with the
sample. Current was measured though the outer wires while the
voltage response was measured across a 1 cm gap between the inner
wires. The AC impedance was measured at 1 kHz, where the impedance
is dominated ionic conductance. The film had conductivity 30 mS/cm
at 80.degree. C.
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